Reshapable hair styling composition comprising acrylic copolymers

ABSTRACT

A reshapable hair styling composition comprising at least one acrylic copolymer comprising: (a) units derived from at least one monomer chosen from (meth)acrylate esters of C 4  to C 18  straight and branched chain alkyl alcohols, (b) units derived from at least one monomer chosen from (meth)acrylate esters of saturated and unsaturated cyclic alcohols containing 6 to 20 carbon atoms, (c) optionally units derived from at least one monomer chosen from hydrophilic monomers, and (d) optionally units derived from at least one monomer other than (a), (b), and (c) monomers, wherein said composition provides a reshapable effect.

The present invention relates to a reshapable hair styling composition.

Fixing the hairstyle is an important element in hair styling, andinvolves maintaining a shaping that has already been carried out, orsimultaneously shaping and fixing the hair.

In accordance with the invention, the term “hair styling composition”relates to any kind of hair composition that can be used to effect hairstyling, for example fixing compositions, shampoos, conditioners,permanent waving compositions, hair care products, and hair treatmentproducts.

The most prevalent hair styling compositions on the cosmetic market forshaping and/or maintaining the hairstyle are spray compositionscomprising a solution, usually alcohol- or water-based, and one or morematerials, generally polymer resins. One of the functions of polymerresins is to form links between the hairs, these materials also beingcalled fixatives, in a mixture with various cosmetic adjuvants. Thissolution is generally packaged either in an appropriate aerosolcontainer, which is pressurized with the aid of a propellant, or in apump flask.

Other known hair styling compositions include styling gels and mousses,which are generally applied to the wetted hair before brushing orsetting it. In contrast to the conventional aerosol lacquers, thesecompositions have the disadvantage that they do not allow the hair to befixed in a shape created before their application. In fact, thesecompositions are essentially aqueous and their application wets the hairand is therefore unable to maintain the initial shape of the hairstyle.In order to shape and fix the hairstyle, therefore, it is necessary tocarry out subsequent brushing and/or drying.

Such hair styling compositions all have the same disadvantage that theydo not allow the hairstyle to be later modified to a desired shape,which is other than that formed initially, without starting the stylingand fixing operations again. Moreover, under various kinds of stress,the hairstyle has a tendency to take on an undesirable permanent set,which cannot easily be modified. Also in the styling process, onedesires hair conditioning benefits, such as ease of combing and softhair feel appearance.

A subject of the invention is a reshapable hair styling compositioncomprising at least one acrylic copolymer comprising: (a) units derivedfrom at least one monomer chosen from (meth)acrylate esters of C₄ to C₁₈straight and branched chain alkyl alcohols, (b) units derived from atleast one monomer chosen from (meth)acrylate esters of saturated andunsaturated cyclic alcohols containing 6 to 20 carbon atoms, (c)optionally units derived from at least one monomer chosen fromhydrophilic monomers, and (d) optionally units derived from at least onemonomer other than (a), (b), and (c) monomers, wherein said compositionprovides a reshapable effect.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one acrylic copolymer comprising: (a)from about 10 to about 85 weight percent of units derived from at leastone monomer chosen from (meth)acrylate esters of C₄ to C₁₈ straight andbranched chain alkyl alcohols, (b) from about 5 to about 70 weightpercent of units derived from at least one monomer chosen from(meth)acrylate esters of saturated and unsaturated cyclic alcoholscontaining 6 to 20 carbon atoms, (c) from 0 to about 20 weight percentof units derived from at least one monomer chosen from hydrophilicmonomers, and (d) optionally units derived from at least one monomerother than (a), (b), and (c) monomers, wherein said composition providesa reshapable effect.

The weight percentages of the (a), (b), and, if used, (c) monomers, arebased on the total weight of the monomers used.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one acrylic copolymer, as describedabove, wherein said reshapable hair styling composition is in the formof a spray, aerosol, mousse, gel, or lotion.

Another subject of the invention is an aerosol device comprising avessel, which comprises: (1) an aerosol composition, which provides areshapable effect and comprises a liquid phase comprising at least onecomposition comprising at least one acrylic copolymer, as describedabove, and a propellant, and (2) a dispenser.

Another subject of the invention is a method of cosmetically treatinghair, comprising applying to the hair before, during, or after shapingof a hairstyle of said hair a composition comprising at least oneacrylic copolymer, as described above, wherein said composition providesa reshapable effect.

Another subject of the invention is a method of reshaping hair,comprising: (1) applying to the hair before, during, or after theinitial shaping of the hairstyle of a composition comprising at leastone acrylic copolymer, as described above, wherein said compositionprovides a reshapable effect, and (2) thereafter shaping the hairstyleat least once, wherein no additional composition or heat is added.

Another subject of the invention is a reshapable hair stylingcomposition comprising at least one acrylic copolymer comprising: (a)from about 20 to about 80 weight percent of units derived from ethylhexyl (meth)acrylate, (b) from about 5 to about 65 weight percent ofunits derived from isobornyl acrylate, and (c) from about 1 to about 15weight percent of units derived from (meth)acrylic acid, wherein theratio of ethyl hexyl (meth)acrylate derived units to isobornyl acrylatederived units ranges from about 0.5:1 to about 6:1, wherein saidcomposition provides a reshapable effect.

In one embodiment of the invention, such reshapable hair stylingcompositions may be in the form of an aqueous emulsion or dispersion.All emulsions comprise a continuous phase and at least one dispersedphase. The term “dispersion” means generally a multi-phase system whereat least one phase contains discrete particles distributed throughout abulk substance. In this invention, at least a portion of the polymer mayexist as the discrete particle in an aqueous phase. Dispersions arepossible through the use of certain components that are insoluble in thewater system. By “dispersion,” it is also meant that not necessarily theentire polymer needs to be water insoluble; some of the polymer can besoluble in the water mixture. It is preferable that the dispersionremains stable under ambient conditions.

The term “(meth)acrylate” is used to mean both acrylate andmethacrylate.

The term “reshapable” hair styling composition means a hair stylingcomposition providing hair styling that can be restored or modifiedwithout new material or heat being applied. For example, in order torestore or modify the hairstyle in case of “drooping” or loss of setting(dishevelment), no new materials, such as water or any form of fixingagent, or heat are required. Thus, to provide a “reshapable” effectmeans to provide a hair styling that can be restored or modified withoutnew material or heat being applied. The efficacy of the composition canbe long lasting, such as 10-24 hours, giving rise to a durable stylingeffect. Other terms, which may be synonymous with reshapable, includerepositionable, remoldable, restyleable, rearrangable, and remodelable.

The (a) monomers constitute from about 10 to about 85 weight percent ofthe total amount of monomers used. In one embodiment, they mayconstitute from about 20 to about 80 weight percent of the total amountof monomers used. The (a) monomers may be chosen from (meth)acrylateesters of C₄ to C₁₈ straight and branched chain alkyl alcohols. In oneembodiment, the (a) monomers may be chosen from isooctyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,2-methylbutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl(meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate,octadecyl (meth)acrylate, and mixtures thereof. In another embodiment,the (a) monomers may be chosen from 2-ethylhexyl acrylate, n-butylacrylate, isooctyl acrylate, 2-methylbutyl acrylate, and mixturesthereof.

The (b) monomers generally have a higher T_(g) than the (a) monomers.They may constitute from about 5 to about 70 weight percent of the totalamount of monomers used. In one embodiment, they may constitute fromabout 10 to about 70 weight percent of the total amount of monomersused. In another embodiment, they may constitute from about 5 to about65 weight percent of the total amount of monomers used. The (b) monomersmay be chosen from (meth)acrylate esters of saturated and unsaturatedcyclic alcohols containing 6 to 20 carbon atoms. In one embodiment, the(b) monomers may be chosen from monofunctional (meth)acrylate esters ofbridged cycloalkyl alcohols, having 6 to 20 carbon atoms, and aromaticalcohols. The cycloalkyl and aromatic groups may be substituted bygroups chosen from C₁ to C₆ alkyl, halogen, cyano groups, and the like.In another embodiment, the (b) monomers are chosen frombicyclo[2.2.1]heptyl (meth)acrylate; adamantyl (meth)acrylate;3,5-dimethyladamantyl (meth)acrylate; isobornyl (meth)acrylate; tolyl(meth)acrylate; phenyl (meth)acrylate; t-butylphenyl (meth)acrylate;2-napthyl (meth)acrylate; benzyl methacrylate; cyclohexyl methacrylate;menthyl methacrylate; 3,3,5-trimethylcyclohexyl methacrylate;dicyclopentenyl (meth)acrylate; 2-(dicyclopentenyloxy)ethyl(meth)acrylate; and mixtures thereof.

The (c) monomers may be hydrophilic monomers. They may constitute from 0to about 20 weight percent of the total amount of monomers used. In oneembodiment, they may constitute from about 1 to about 15 weight percentof the total amount of monomers used. In another embodiment, they mayconstitute from 1 to about 10 weight percent of the total amount ofmonomers used. In one embodiment, the (c) monomers may be chosen fromthose monomers having hydroxyl, ether, amide, amine, carboxylic acid,sulfonic acid, and phosphonic acid functionalities. In anotherembodiment, the (c) monomers may be chosen from (meth)acrylamide,2-ethoxyethyl (meth)acrylate, mono (meth)acrylates of polyethyleneglycol monoethers, N-vinyl-2-pyrrolidone, N-vinyl formamide, N-vinylacetamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl acrylate, vinylpyridine, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl(meth)acrylate, N-t-butylaminoethyl acrylate, acrylic acid, methacrylicacid, itaconic acid, maleic acid, fumaric acid, vinyl benzoic acid,2-carboxyethyl acrylate, 2-sulfoethyl (meth)acrylate, and 4-vinyl phenylphosphonic acid. In yet another embodiment, the (c) monomers may bechosen from (meth)acrylic acid and N-vinyl-2-pyrrolidone.

The copolymer may optionally include units derived from other monomersto improve performance, reduce cost, or for other purposes, providedthat such monomers are used in an amount that does not compromise thecomposition's reshapable effect. Examples of such other monomers mayinclude vinyl esters, vinyl chlorides, vinylidene chlorides, styrenes,macromolecular monomers such as monoacrylic functional polystyrene andpolydimethylsiloxane, and the like.

The composition may further comprise an appropriate cosmeticallyacceptable vehicle. The choice of vehicle is adapted to the method ofapplication selected. The cosmetic vehicle appropriate for hair may bechosen from water, water miscible solvents such as lower alcohols, e.g.,C₁ to C₄ branched and straight chain aliphatic alcohols, andcombinations thereof. In one embodiment, the vehicle is a lower alcoholchosen from ethanol, n-propanol, and 2-propanol (IPA). When watermiscible solvents and water are present, the solvent to water ratio mayrange from about 20:80 to about 90:10 weight/weight, such as from about30:70 to about 85:15.

The vehicle may also comprise additional solvents. For example, otherrapid evaporating solvents may be used, such as hexamethyldisiloxane(HMDS); cyclic silicones (D₄ and D₅); C₄-C₁₀ alkanes includingisoparafins such as Permethyl 97A and Isopar C; acetone;hydrofluoroethers (HFEs) and the like.

The composition may also comprise additives such as gelling agents,foaming agents, and silicones. It is understood that the person skilledin the art will know how to choose the additional constituents and theiramount in the composition according to the invention, such as theconstituents of the composition, so as not to adversely affect orsubstantially affect its reshapable hair styling properties.

The inventive copolymers of the present invention may be prepared usingemulsion polymerization, solution polymerization followed by aninversion step, and suspension polymerization. These methods useinitiators that, through various techniques, are decomposed to form freeradicals. Once in their radical form, the initiators react with themonomers, starting the polymerization process. The initiators are oftencalled “free radical initiators.” Various decomposition methods for theinitiators are discussed first, followed by a description of theemulsion, solution, and suspension polymerization methods.

The initiator can be decomposed homolytically to form free radicals.Homolytic decomposition of the initiator can be induced by using heatenergy (thermolysis), using light energy (photolysis), and/or usingappropriate catalysts. Light energy can be supplied by means of visibleor ultraviolet sources, including low intensity fluorescent black lightlamps, medium pressure mercury arc lamps, and germicidal mercury lamps.

Catalyst induced homolytic decomposition of the initiator typicallyinvolves an electron transfer mechanism, resulting in areduction-oxidation (redox) reaction. This redox method of initiation isdescribed in Elias, Chapter 20 (detailed below). Initiators such aspersulfates, peroxides, and hydroperoxides are more susceptible to thistype of decomposition. Useful catalysts include, but are not limited to(1) amines, (2) metal ions used in combination with peroxide orhydroperoxide initiators, and (3) bisulfite or mercapto-based compoundsused in combination with persulfate initiators.

Presently, in certain embodiments of the invention, the method ofinitiation comprises thermolysis or catalysis. Thermolysis can provideease of control of the reaction rate and exotherm.

Useful initiators are described in Chapters 20 & 21 Macromolecules, Vol.2, 2nd Ed., H. G. Elias, Plenum Press, 1984, New York, the disclosure ofwhich is specifically herein by reference. Useful thermal initiatorsinclude, but are not limited to, the following: (1) azo compounds suchas 2,2-azo-bis-(isobutyronitrile), dimethyl 2,2′-azo-bis-isobutyrate,azo-bis-(diphenyl methane), and 4-4′-azo-bis-(4-cyanopentanoic acid);(2) peroxides such as benzoyl peroxide, cumyl peroxide, tert-butylperoxide, cyclohexanone peroxide, glutaric acid peroxide, lauroylperoxide, and methyl ethyl ketone peroxide; (3) hydrogen peroxide andhydroperoxides such as tert-butyl hydroperoxide and cumenehydroperoxide; (4) peracids such as peracetic acid and perbenzoic acid;potassium persulfate; ammonium persulfate; and (5) peresters such asdiisopropyl percarbonate.

Useful photochemical initiators include but are not limited to benzoinethers such as diethoxyacetophenone, oximino-ketones, acylphosphineoxides, diaryl ketones such as benzophenone and 2-isopropylthioxanthone, benzil and quinone derivatives, and 3-ketocoumarins asdescribed by S. P. Pappas, J. Rad. Cur., July 1987, p. 6, the disclosureof which is specifically incorporated herein by reference.

In one embodiment, the copolymers of the present invention can be madeby emulsion polymerization, generally comprising a process where themonomers are dispersed in a continuous phase (typically water) with theaid of an emulsifier and polymerized with free-radical initiators,described above. Other components that are often used in this processinclude stabilizers (e.g., copolymerizable surfactants), chain transferagents for minimizing and/or controlling the polymer molecular weight,and catalysts. The product of this type of polymerization is typically acolloidal dispersion of the polymer particles, often referred to as a“latex.” In one embodiment of an emulsion polymerization process, aredox chemistry catalyst, such as sodium metabisulfite, used incombination with potassium persulfate initiator and ferrous sulfateheptahydrate, is used to start the polymerization at or near roomtemperature. Typically, the copolymer particle size is less than onemicrometer, such as less than 0.5 micrometer.

In another embodiment, the copolymers of the present invention can bemade by solution polymerization followed by an inversion step. In oneillustrative solution polymerization method, the monomers and suitableinert solvents are charged into a reaction vessel. The monomers and theresultant copolymers are soluble in the solvent. After the monomers arecharged, an initiator, such as a thermal free radical initiator, isadded. The vessel is purged with nitrogen to create an inert atmosphere.The reaction is allowed to proceed, typically using elevatedtemperatures, to achieve a desired conversion of the monomers to thecopolymer. In solution polymerization, the initiator used may comprise athermally decomposed azo or peroxide compound for reasons of solubilityand control of the reaction rate.

Suitable solvents for solution polymerizations include but are notlimited to (1) esters such as ethyl acetate and butyl acetate; (2)ketones such as methyl ethyl ketone and acetone; (3) alcohols such asmethanol and ethanol; (4) aliphatic and aromatic hydrocarbons; and (5)mixtures thereof. The solvent may be any substance which is liquid in atemperature range of about −10° C. to about 50° C., does not interferewith the energy source or catalyst used to dissociate the initiator toform free radicals, is inert to the reactants and product, and will nototherwise adversely affect the reaction. The amount of solvent, whenused, is generally about 30 to about 80 percent by weight based on thetotal weight of the reactants and solvent. Preferably, the amount ofsolvent ranges from about 40 weight percent to about 65 weight percent,based upon the total weight of the reactants and solvent, to yield fastreaction times.

Copolymers prepared by solution polymerization can be inverted to yielddispersions of small average particle size, typically less than aboutone micrometer, such as less than about 0.5 micrometer. Inversion canoccur in an aqueous carrier or aqueous solvent provided that (1) theycontain ionic functionality or (2) they contain acidic or basicfunctionality, which on neutralization yields ionic functionality.

Copolymers containing acidic functionality are obtained bycopolymerizing acidic monomers. Suitable acidic monomers include thosecontaining carboxylic acid functionality such as acrylic acid,methacrylic acid, itaconic acid, etc.; those containing sulfonic acidfunctionality such as 2-sulfoethyl methacrylate; and those containingphosphonic acid functionality. Preferred acidic monomers include acrylicacid and methacrylic acid.

Copolymers containing basic functionality are obtained by copolymerizingbasic monomers. Suitable basic monomers include those containing aminefunctionality such as vinyl pyridine; N,N-diethylaminoethyl(meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate; andN-t-butylaminoethyl acrylate. Preferred basic monomers includeN,N-dimethylaminoethyl (meth)acrylate.

Preferably the copolymer is prepared in a water-miscible solvent, whichhas a boiling point below 100° C., such as acetone or methyl ethylketone. Alternatively, a non-water-miscible polymerization solvent suchas ethyl acetate may be used. The non-water-miscible polymerizationsolvent may be removed from the copolymer by using a rotary evaporator.The resulting copolymer can then be dissolved in a water-misciblesolvent such as those described above or mixtures including isopropanol,methanol, ethanol, and tetrahydrofuran.

The resulting solutions are added with stirring to an aqueous solutionof a base (in the case of copolymers containing the acidicfunctionality) or an acid (in the case of copolymers containing thebasic functionality). Alternatively, the base or acid can be added tothe polymer solution prior to adding water or being added to water.Suitable bases include (1) ammonia and organic amines, such asaminomethyl propanol, triethyl amine, triethanol amine, methyl amine,and morpholine, and (2) metal hydroxides, oxides, and carbonates, etc.Suitable acids include (1) carboxylic acids such as acetic acid, and (2)mineral acids, such as HCl. In the case of a volatile weak base (e.g.,ammonia) or acid (e.g., acetic acid), the ionic group formed (anammonium carboxylate) is non-permanent in nature. For example, for anacrylic acid containing polymer neutralized with aqueous ammonia, thepolymer remains as the ammonium acrylate derivative when dispersed inwater, but is thought to revert to its original free acid state as thecoating dries on the surface. This is because there is equilibriumbetween the neutralized and free acid, which is shifted towards the freeacid as the ammonia is driven off on drying.

In yet another embodiment, the copolymers of the present invention canbe made by a suspension polymerization method. The suspensionpolymerization method for making the inventive copolymers can proceed inthe absence of surfactants. Instead, colloidal silica in combinationwith a promoter may be used as the stabilizer. Using this process,surfactant-free copolymers can be obtained with a relatively narrowparticle size distribution (preferably, no greater than about 20%).

In one embodiment, the method for suspension polymerization involvesmaking a monomer premix comprising the (a), (b), and optional (c) and(d) monomers. The premix is combined with a water phase, such asdeionized water, containing colloidal silica and a promoter. Amphiphilicpolymers represent one class of useful promoters.

The pH of the mixture is adjusted so as to be in the range of 3 to 11,such as in the range of 4 to 6, without coagulation of the particles.For certain monomers, the initial pH of the mixture can be as low asabout 2.5. This pH is low enough for the colloidal silica to stabilizethe monomer droplet, but the final product may contain a small amount ofcoagulum. Similar observations can be made at high pH. It has beenobserved that when the mixture is treated with ammonia or hydrochloricacid to a pH ranging from about 4 to about 6, the reaction is morestable and the final product is basically free of coagulum.

The mixture is exposed to high shear, such as that capable in a Waring™blender, to break the monomer droplets down to a diameter size of 1micrometer or less. The shearing action is then reduced to a loweragitation (or temporarily stopped) to allow for the partial coalescenceof the small droplets and formation of a suspension. Initiator is added.The silica-promoter mixture stabilizes the droplets and limits theircoalescence yielding very uniform, and sometimes nearly monodisperseparticles. The suspension polymerization is completed under moderateagitation and a stable, aqueous dispersion of acrylic particles isobtained.

The above described suspension polymerization has several advantages.For example, the method yields a copolymer with a narrow distribution ofmean particle size and limited coalescence. When coalescence is present,the particles tend to migrate towards one another and can form largemasses. Coalescence hampers the handling and transportation of theparticles and thus is undesirable.

Also, the method allows for copolymers that withstand freezingtemperatures, allowing them to be redispersed after thawing. It has beendiscovered that the copolymer is stable, i.e., does not coalesce whenthe same volume of alcohol (methanol or isopropanol) and water is usedin the dispersion.

In another embodiment of the invention, the acrylic polymer has a glasstransition temperature (Tg) ranging from about −100° C. to about 15° C.According to the present invention, the Tg of the acrylic polymer isobtained following the application of the acrylic copolymer in a simplexvehicle to a substrate and then drying. The glass transition temperatureis determined by the Differential Scanning Calorimetric method (DSC).

In one embodiment of the invention, the acrylic copolymer may be presentin an amount ranging from about 0.1 to about 40, such as from about 0.5to about 15, weight percent of the total weight of the composition inorder to provide a reshapable effect.

The composition according to the invention may comprise at least oneother constituent, which is conventional in cosmetics, chosen frompreservatives; perfumes; UV filters; active haircare agents;plasticizers; anionic, cationic, amphoteric, nonionic, and zwitterionicsurfactants; hair conditioning agents such as silicone fluids, fattyesters, fatty alcohol, long chain hydrocarbons, emollients, lubricants,and penetrants such as lanolin compounds, protein hydrolysates, andother protein derivatives; anionic, cationic, amphoteric, nonionic, andzwitterionic polymers; dyes; tints; bleaches; reducing agents; pHadjusting agents; sunscreens; and thickening agents.

The compositions according to the invention can be provided in any formknown from the prior art, which is appropriate for their application tothe hair, including in the form of a vaporizable composition such assprays and aerosols, mousse, gel, or lotion.

The composition may be in any of the conventional forms of cosmeticcomposition including, but not limited to, shampoos, hair rinses,permanent waving compositions, waving compositions, hair dyecompositions, hair straightening compositions, hair fixing products,hair styling gel products, products to use before or after a hair dyetreatment, products to use before or after a permanent waving treatment,hair straightening compositions, products to use before or after a hairstraightening treatment, and fixing foams.

The composition according to the invention may be vaporizable, forexample by a pump, or may be a pressurized aerosol composition. It maybe vaporizable by a dispensing valve controlled by a dispensing head,which in turn comprises a nozzle, which vaporizes the aerosolcomposition. A vaporizable composition according to the inventioncomprises an appropriate solvent. Advantageously, the appropriatesolvent comprises at least one solvent chosen from water and loweralcohols. In accordance with the invention, the term lower alcohol meansa C₁ to C₄ aliphatic alcohol, preferably ethanol.

When the vaporizable composition according to the invention is anaerosol composition, it additionally comprises an appropriate amount ofpropellant. The propellant comprises compressed or liquefied gases,which are normally employed for the preparation of aerosol compositions.Suitable gasses include compressed air, carbon dioxide, nitrogen, andgases, which are soluble or otherwise in the composition, such asdimethyl ether, fluorinated or non-fluorinated hydrocarbons, andmixtures thereof.

The present invention additionally provides an aerosol device comprisinga vessel comprising an aerosol composition, which comprises on the onehand a liquid phase (or juice) comprising at least one hair stylingmaterial as described above in an appropriate medium and on the otherhand a propellant, and a dispenser for dispensing said aerosolcomposition.

The present invention additionally provides a method of treatingkeratinous fibers, especially hair, in which the composition accordingto the invention as defined above is applied to the hair before, during,or after the shaping of the hairstyle.

The compositions according to the invention can be rinsed off or notrinsed off the hair.

The present invention additionally provides the use of a composition asdefined above in, or for the preparation of, a cosmetic reshapable hairstyling formulation.

The determination of whether a composition with an acrylic copolymeraccording to the invention can provide a reshapable effect can bedetermined by an in vivo test.

Where the composition is in the form of a lotion, for example, the invivo test proceeds as follows. The hair of the model is washed and thendivided into two symmetrical portions, the right and the left sides. Thecomposition is applied to one side of the head of the model, while areference composition is applied to the other side of the head. Thereference composition may, for example, be chosen from water, anexisting commercial product, or another composition under study. Thehairdresser dries and styles both sides of the head. The two sides ofthe head are separately evaluated for the styling effect, the cosmeticproperties, and the reshapable effect. For example, once dried, the hairis brushed in different directions to remove the original styling. Thehair is then brushed to restore the original styling. The process ofremoving the styling, restoring the styling, and evaluating the successof restoring the styling is repeated at least one more time to determinewhether the composition is a reshapable hair styling composition. Areshapable hair styling composition permits (1) the original hairstyling to be restored after brushing and (2) the creation of a new hairstyling after brushing, which may also be restored after brushing. Ifthe composition to be evaluated is in another form, such as a shampoo orconditioner, the in vivo test can be appropriately modified by oneskilled in the art.

It is understood that the person skilled in the art would recognize thatnot all formulations would provide reshapable effect for all hair typesduring in vivo testing and will know how to formulate and evaluatereshapable hair styling composition in view of the various hairparameters, such as length (short versus long), diameter (thin versusthick), structure (curly versus straight), condition (oily, dry, ornormal); and whether the hair is colored, bleached, permed, orstraightened. Thus, in vivo testing may require testing on 10-20different individuals.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The invention may be understood more clearly with the aid of thenon-limiting examples that follow, and which constitute an advantageousembodiment of the compositions in accordance with the invention.

EXAMPLES

Hair compositions according to the invention were produced withdifferent acrylic copolymers. Percentages given are by weight, unlessotherwise specified

1) Preparation of the Acrylic Copolymers

Examples 1 to 13 Copolymers Made by Emulsion Polymerization

Into a one liter Mortonized split resin flask was charged 100 grams ofmonomers (detailed in Table I below), 80 milligrams of carbontetrabromide, 124.7 grams of deionized water, 200 milligrams ofpotassium persulfate, 64 milligrams of sodium metabisulfite, 1 gram ofsodium dodecyl benzene sulfonate, and 2.5 g of Mazon SAM 211 alkylenepolyalkoxy ammonium sulfate copolymerizable surfactant (available fromPPG Industries, Pittsburgh, Pa.). The head was placed on the flask and athermocouple, nitrogen inlet, and mechanical stirrer attached. Theheadspace was swept with nitrogen at 1 liter per minute while heatingthe contents with infrared lamps to about 30° C. and stirring at 250rpm. About 1 gram of a solution of 28 milligrams ferrous sulfateheptahydrate in 50 grams deionized water was charged, the flask sealed,and a vacuum pulled on the flask three times, breaking it each time withnitrogen. After 15 or 20 minutes an exotherm is noted which peaks 20 to25 minutes later at 55° C. to 65° C. Reactor temperature is increased toabout 75° C. and held for one hour, then the resulting latex wasfiltered through doubled over cheesecloth into a jar. In all casesmoderate levels of coagulum were noted around the thermocouple andstirring paddle. TABLE I Monomer Charges Used for EmulsionPolymerization Example g 2-EHA g IBOA g AA g MAA 1 60 35 0 5 2 55 40 0 53 50 45 5 0 4 50 45 0 5 5 50 40 0 10 6 45 50 5 0 7 45 50 0 5 8 35 60 0 59 70 25 0 5 10 60 35 5 0 11 55 40 5 0 12 25 70 0 5 13 80 15 5 02-EHA = 2-ethylhexyl acrylateIBOA = isobornyl acrylateAA = acrylic acidMAA = methacrylic acid

Examples 14 to 17 Copolymers Made by Solution Polymerization andInversion in Water

Into a 120 milliliter glass bottle was charged 24 grams of monomers(detailed in Table II below), 120 milligrams of carbon tetrabromide, 36grams of methylethyl ketone, and 72 milligrams ofazobis(isobutyronitrile). The contents of the bottle were swept withnitrogen at about 1 liter per minute for two minutes, then the bottlewas capped and tumbled in a water bath for 24 hours at about 55° C.yielding a moderate viscosity solution. 15 grams (containing 6 grams ofpolymer or 8.3 milliequivalents of carboxylic acid) of the resultingsolution was charged into a 250 milliliter round bottom flask containinga solution of 0.67 grams (7.5 milliequivalents, 90% neutralization) of2-amino-2-methyl-1-propanol in 14 grams of deionized water with moderateagitation. The solvent was removed from the resulting dispersion by arotary evaporator set at about 63° C. at a reduced pressure of 40kilopascals yielding a milky white dispersion. The resulting dispersionswere coated as described above. TABLE II Monomer Charges Used forSolution Polymerization with Inversion Example g 2-EHA g IBOA g CHXMA gAA 14 12.6 9.0 0 2.4 15 11.4 10.2 0 2.4 16 10.8 0 10.8 2.4 17 8.4 0 13.22.4CHXMA = cyclohexyl methacrylate

Example 18 to 20 Copolymers Made by Suspension Polymerization

In a one liter Mortonized split resin flask was charged 240 gram of amonomer mixture (detailed in Table III). Added to the flask was 6.9 gLudox™ 50 (50% by wt colloidal silica in water, available from Aldrich,Milwaukee, Wis.), 360 g deionized water, 0.42 g adipic acid/diethanolamine condensate (a 50% solids used as a promoter, prepared according tothe procedure disclosed in U.S. Pat. No. 5,238,736), and 0.08 gpotassium dichromate. The head was placed on the flask and athermocouple, nitrogen inlet, and mechanical stirrer attached. Theentire content inside the flask is mixed. The pH is measured andadjusted by adding ammonium hydroxide to a pH between 4 and 5. Themixture was then transferred to a Warring™ blender and exposed to highshear (about 22,000 rpm) for six minutes total, using shear for abouttwo minutes at a time to avoid overheating the mixture.

The mixture was then returned to the Mortonized flask and 0.36 g ofVazo™ 64 (azo-bis(isobutyronitrile) initiator, available from E.I. duPont de Nemours & Co., Wilmington, Del.) was added. A nitrogen purge wasstarted and the mixture is agitated gently for several minutes to letthe initiator dissolve. The agitation speed is adjusted to about 300 rpmand the temperature was set at about 60° C. The reaction started withinminutes and was allowed to exotherm. After exotherming, the temperaturewas maintained at about 60° C. for about four hours. TABLE III MonomerCharges Used for Suspension Polymerization Example Parts g 2-EHA g IBOAg MAA 18 50/45/5 120 108 12 19 55/40/5 132 96 12 20 60/35/5 144 84 12

Example 21

A 50/50 mixture of the emulsion from Example 19 and a dispersioncomprising AQ 1350 by the Eastman Chemical Co. as disclosed in WO98/38969 can be made.

Example 22

A 25/75 mixture of the emulsion from Example 19 and the emulsion fromExample 20 can be made.

2) Preparation of the Hair Styling Compositions

Eleven hair styling compositions in accordance with the invention wereprepared using the components and amounts in weight percent listedhereafter. The testing was conducted on several models with one part ofthe head receiving a reference composition and the other side of thehead receiving the tested composition. The compositions were applied towet hair after shampooing. The hair was then dried, brushed, andevaluated.

Reference: AQ 1350 4% active material Water qsp 100%

Formulation A: Example 19 4% active material Water qsp 100%

Formulation A imparted good hairstyling with good cosmetic propertiesand a reshapable effect but the latter was not as good as the reference.

Formulation B: Example 13 4% active material Water qsp 100%

Formulation B imparted good hairstyling and a reshapable effect equal tothe reference with adequate cosmetic properties.

Formulation C: Example 9 4% active material Water qsp 100%

Formulation C imparted very good hairstyling and a reshapable effect.The latter and cosmetic properties were not as good as the reference.

Formulation D Example 1 4% active material Water qsp 100%

Formulation D imparted good hairstyling and a reshapable effect equal orbetter than the reference with adequate cosmetic properties.

Formulation E: Example 2 4% active material Water qsp 100%

Formulation E imparted good hairstyling but poor reshapable effect andcosmetic properties compared to the reference.

Formulation F: Example 11 4% active material Water qsp 100%

Formulation F imparted adequate hairstyling and a good reshapable effectbut the hairstyling and cosmetic properties were not as good as thereference.

Formulation G: Example 10 4% active material Water qsp 100%

Formulation G imparted good hairstyling but poor reshapable effect andcosmetic properties compared to the reference.

Formulation H: Example 3 4% active material Water qsp 100%

Formulation H imparted good hairstyling and a reshapable effect betterthan the reference with good cosmetic properties.

Formulation I: Example 1 2% active material Example 3 2% active materialWater qsp 100%

Formulation I imparted very good hairstyling and a very good reshapableeffect with correct cosmetic properties.

Formulation J: Example 1 2% active material Example 10 2% activematerial Water qsp 100%

Formulation J imparts very good hairstyling and very good reshapableeffect with medium cosmetic properties.

Formulation K: Example 2 2% active material Example 3 2% active materialWater qsp 100%

Formulation K imparts very good hair styling and very good reshapableeffect with medium cosmetic properties.

1. A reshapable hair styling composition comprising at least one acryliccopolymer comprising: (a) units derived from at least one monomer chosenfrom (meth)acrylate esters of C4 to C18 straight and branched chainalkyl alcohols, (b) units derived from at least one monomer chosen from(meth)acrylate esters of saturated and unsaturated cyclic alcoholscontaining 6 to 20 carbon atoms, (c) optionally units derived from atleast one monomer chosen from hydrophilic monomers, and (d) optionallyunits derived from at least one monomer other than (a), (b), and (c)monomers, wherein said composition provides a reshapable effect.
 2. Areshapable hair styling composition comprising at least one acryliccopolymer comprising: (a) from about 10 to about 85 weight percent ofunits derived from at least one monomer chosen from (meth)acrylateesters of C4 to C18 straight and branched chain alkyl alcohols, (b) fromabout 5 to about 70 weight percent of units derived from at least onemonomer chosen from (meth)acrylate esters of saturated and unsaturatedcyclic alcohols containing 6 to 20 carbon atoms, (c) from 0 to about 20weight percent of units derived from at least one monomer chosen fromhydrophilic monomers, and (d) optionally units derived from at least onemonomer other than (a), (b), and (c) monomers, wherein said compositionprovides a reshapable effect.
 3. The composition according to claim 2,wherein the composition further comprises a cosmetic vehicle appropriatefor hair.
 4. The composition according to claim 2, wherein said at leastone (a) monomer is chosen from n-butyl (meth)acrylate, isobutylacrylate, t-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isononyl(meth)acrylate, lauryl (meth)acrylate, and octadecyl (meth)acrylate. 5.The composition according to claim 2, wherein said at least one (b)monomer is chosen from bicyclo [2.2.1]heptyl (meth)acrylate, adamantyl(meth)acrylate, 3,5-dimethyladamantyl (meth)acrylate, isobornyl(meth)acrylate, tolyl (meth)acrylate, phenyl (meth)acrylate,t-butylphenyl (meth)acrylate 2-napthyl (meth acrylate, benzylmethacrylate, cyclohexyl methacrylate, menthyl methacrylate,3,3,5-trimethylcyclohexyl methacrylate, dicyclopentenyl (meth)acrylate,and 2-(dicyclopentenyloxy) ethyl (meth)acrylate.
 6. The compositionaccording to claim 2, wherein said at least one (c) monomers is chosenfrom (meth)acrylic acid and N-vinyl-2-pyrrolidone.
 7. The compositionaccording to claim 2, wherein said at least one acrylic copolymer ispresent in an amount ranging from about 0.1 to about 40 weight percentof the total weight percent of the composition.
 8. The compositionaccording to claim 7, wherein the amount of said at least one acryliccopolymer ranges from about 0.5 to about 15 weight percent.
 9. Thecomposition according to claim 2, wherein said at lest one acryliccopolymer has a Tg ranging from about −100° C. to about 15° C.
 10. Thecomposition according to claim 2, wherein the composition furthercomprises at least one additional polymer.
 11. The composition accordingto claim 10, wherein said at least one additional polymer is chosen fromanionic, cationic, amphoteric, nonionic, and zwitterionic polymers. 12.The composition according to claim 2, further comprising at least oneother constituent, which is conventional in cosmetics, chosen frompreservatives, perfumes, UV filters, active haircare agents,plasticizers, anionic, cationic, amphoteric, noinionic, and zwitterionicsurfactants, hair conditioning agents such as silicone fluids, fattyesters, fatty alcohol, long chain hydrocarbons, emollients, lubricantsand penetrants such as lanolin compounds, protein hydrolysates, andother protein derivatives, dyes, tins, bleaches, reducing agents, pHadjusting agents, sunscreens, and thickening agents.
 13. A compositionaccording to claim 2, wherein said reshapable hair styling compositionis in the form of a spray, aerosol, mousse, gel, or lotion.
 14. Anaerosol device comprising a vessel, which comprises: (1) an aerosolcomposition, which provides a reshapable effect and comprises a liquidphase comprising at least one composition according to claim 2 and apropellant, and (2) a dispenser.
 15. A method of cosmetically treatinghair, comprising applying to the hair before, during, or after shapingof a hairstyle of said hair a composition according to claim 2, whereinsaid composition provides a reshapable effect
 16. A method of reshapinghair, comprising: (1) applying to the hair before, during, or after theinitial shaping of the hairstyle of a composition according to claim 2,wherein said composition provides a reshapable effect, and (2)thereafter shaping the hairstyle at least once, wherein no additionalcomposition or heat is added. 17-27. (canceled)